A protective one-coat water-based coating based on dip coating and a process for its preparation

Abstract

The application belongs to the technical field of water-based paint and particularly relates to a protective one-coat water-based paint based on dip coating and a preparation process thereof. The water-based paint comprises an A component and a B component. The A component comprises the following raw materials in parts by weight: 50-70 parts of a main body resin, 4-14 parts of water, 0.3-0.7 parts of a water-based wet dispersing agent, 0.05-0.06 parts of a defoaming agent, 22-28 parts of a filler, 2-3 parts of a water-based additive, 0.7-1.2 parts of an anti-aging additive, 3-6 parts of an anti-rust pigment, 0.5-0.8 parts of a rheological additive, and 0.5-1 part of a thickening agent. The main body resin is a water-based epoxy ester resin, an amino resin and a water-based fluorocarbon resin. The B component comprises a curing agent. The application aims at improving the anti-aging and salt fog resistance of the existing water-based paint, improving the anti-aging and salt fog resistance, and preparing a one-coat water-based paint with reduced coating process and energy consumption.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of water-based paint, and particularly relates to a protective one-coat water-based paint based on dip coating and a preparation process thereof. BACKGROUND

[0002] With the development of the motorcycle industry and the material field in recent years, the corresponding motorcycle frame industry has also developed vigorously, in addition, it has also driven the development of related industries such as the paint industry. At present, the traditional motorcycle frame coating process mainly adopts a spraying mode. However, due to the uneven shape and complex structure of the motorcycle frame, the coating process has high energy consumption, and uniform spraying on the frame surface is often impossible by using the spraying mode. In addition, this process is quite time-consuming and labor-intensive, and uneven spraying affects the performance.

[0003] At present, in the field of water-based paint, water-based epoxy ester paint is widely used due to its good adhesion, chemical resistance and other characteristics. Epoxy ester has the excellent properties of both epoxy systems and drying oils, but has the problems of slow film drying speed, poor weather resistance and salt fog resistance, and the paint film is prone to blistering and rusting in a salt fog environment, which affects the protection effect and service life of the coating, and also has the problems of insufficient alkali resistance and aging resistance.

[0004] Therefore, it is imperative to provide a one-coat water-based paint with excellent protective properties such as aging resistance and salt fog resistance, and to reduce the coating process and energy consumption. SUMMARY

[0005] In view of the problems of insufficient aging resistance and salt fog resistance of the existing water-based paint, which affect the protection effect and service life of the coating, the application provides a protective one-coat water-based paint based on dip coating and a preparation process thereof.

[0006] In a first aspect, the application provides a protective one-coat water-based paint based on dip coating, which adopts the following technical solution:

[0007] A protective one-coat water-based paint based on dip coating, the water-based paint comprising A component and B component; the A component comprises the following raw materials by weight: 50-70 parts of main body resin, 4-14 parts of water, 0.3-0.7 parts of water-based wet dispersant, 0.05-0.06 parts of defoaming agent, 22-28 parts of filler, 2-3 parts of water-based auxiliary agent, 0.7-1.2 parts of aging resistance auxiliary agent, 3-6 parts of anti-rust pigment, 0.5-0.8 parts of rheological auxiliary agent, and 0.5-1 part of thickening agent; the main body resin is water-based epoxy ester resin, amino resin and water-based fluorocarbon resin; the B component comprises a curing agent.

[0008] By adopting the technical scheme, through the joint action of the main resin being the water-based epoxy ester resin, the amino resin and the water-based fluorocarbon resin, the water-based epoxy ester resin containing the epoxy group and the ester group structure can occur cross-linking reaction with the amino group in the amino resin to form a stable three-dimensional network structure, which not only significantly improves the salt spray resistance of the coating, but also makes the coating have good adhesion and chemical resistance, and optimizes the surface leveling property of the coating, so that the coating film surface is smoother and more uniform, and the appearance of the water-based coating is improved. In addition, the water-based fluorocarbon resin contains fluorocarbon bonds with strong chemical stability, which can effectively resist ultraviolet radiation, thereby greatly improving the aging resistance of the coating. In addition, the active groups of the water-based epoxy ester resin and the hydroxyl groups in the water-based fluorocarbon resin are further cross-linked to enhance the overall density of the coating, reduce the thickness of the coating film while ensuring the excellent protective performance of the coating. This composite system not only realizes the function of one coat, but also meets the requirements of low energy consumption and high protection. Combined with the specific ratio of fillers, anti-rust pigments and anti-aging additives, a one coat coating with excellent comprehensive performance is formed. The main resin used in combination not only provides the coating with good adhesion and chemical resistance, enhances the hardness and heat resistance of the coating film, but also improves the weather resistance and pollution resistance of the coating; the addition of fillers improves the flatness and mechanical properties of the coating film; the anti-aging additive effectively absorbs ultraviolet rays and delays the aging process, thereby improving the service life of the coating; the anti-rust pigment can prevent metal surface corrosion and enhance the corrosion resistance. The components in the present application cooperate with each other to significantly improve the protective performance of the coating, which can be used for dip coating, reduces the complexity of the coating process and energy consumption, and is suitable for coating of complex structures such as motorcycle frames.

[0009] In a specific embodiment, the water-based epoxy ester resin is a modified water-based epoxy ester resin, and the preparation method of the modified water-based epoxy ester resin is as follows: (1) mixing epoxy resin and molecular weight regulator with linoleic acid, stirring at 130-150℃ for 3-5min, and cooling to 80-90℃ to obtain an epoxy ester prepolymer;

[0010] (2) first mix 6-8 parts by mass of VPA and 4-5 parts by mass of HEA, add 0.4-0.6 parts by mass of APS, pre-emulsify for 10-15min, then slowly drop 80-90 parts by mass of the epoxy ester prepolymer obtained in step (1), react at 80-90℃ for 2-3h, then add 8-11 parts by mass of KH570 and 2-3 parts by mass of VPA, followed by adding 0.2-0.4 parts by mass of APS, heat to 80-85℃ and react for 1-2h, cool to 50℃, adjust the pH to 8-9, and adjust the solid content to 40-45%.

[0011] The mass ratio of the epoxy ester prepolymer to VPA is (6-8):1.

[0012] Preferably, the mass ratio of the epoxy resin and linoleic acid is (4-6):1.

[0013] By adopting the above technical scheme, the epoxy resin and linoleic acid form an epoxy ester prepolymer with a long-chain fatty acid structure under the action of the molecular weight regulator, which increases the flexibility of the molecular chain, helps to improve the leveling property of the water-based paint, thereby improving the flexibility and gloss of the coating film, and obtaining better appearance effect. If the content of the epoxy resin is too low, it may reduce the uniformity of the subsequent reaction and the performance of the coating film. The subsequent addition of APS (ammonium persulfate) promotes the active sites on the epoxy ester prepolymer, the free radical chain growth between HEA (hydroxyethyl acrylate) and VPA (vinyl phosphate monomer), and the introduction of polymer segments containing phosphate ester side chains can form coordination bonds with the metal substrate, thereby enhancing the chemical bonding between the coating and the substrate. HEA provides crosslinking active sites to improve the adhesion and salt spray resistance of the coating, thereby enhancing the rheological property of the water-based coating, suitable for low film thickness film formation in the dip coating process, and can inhibit the penetration of corrosion media (such as Cl-, H2O). Again, the initiator APS and the silane coupling agent KH570 are grafted, and the siloxane condenses slightly during hydrolysis to balance the hardness and flexibility, thereby enhancing the coating density and avoiding brittle cracking. The second addition of VPA further supplements the unreacted sites, reduces coating pore defects, and improves salt spray resistance and barrier properties. And VPA is added twice, which can make the phosphate ester uniformly distributed, avoid local excess leading to agglomeration, and thereby affect the surface properties of the material, affecting the leveling property and stability of the paint and other coating properties.

[0014] In a specific implementation scheme, the mass ratio of the water-based epoxy ester resin, amino resin and water-based fluorocarbon resin is (6.6-7.2):1:(0.5-0.8).

[0015] By adopting the above technical scheme, the water-based epoxy ester resin, amino resin and water-based fluorocarbon resin in the proportion range of the present application jointly act to further enhance the overall protective performance of the coating film, especially the aging resistance and salt spray resistance, effectively prolonging the service life of the coating. Not only does it retain the original excellent adhesion and chemical resistance of the epoxy resin, but also introduces an acrylic monomer to improve the drying speed and weather resistance of the coating film, and a siloxane to improve the salt spray resistance and barrier properties, avoid brittle fracture, and the phosphate ester group and the -CF3 group of the fluorocarbon resin can synergistically block the penetration of water and oxygen, so that a modified water-based epoxy ester resin content that is too low will reduce the adhesion, salt spray resistance and leveling property of the water-based paint, thereby affecting the coating performance and long-term protective performance of the material. If the content of the amino resin is too low, it will affect the crosslinking with the water-based epoxy ester resin to form a stable three-dimensional network structure, thereby reducing the hardness of the material and the surface performance of the coating film.

[0016] The filler includes one or more of carbon black, zinc oxide, talc, and barium sulfate.

[0017] Preferably, the mass ratio of the carbon black, zinc oxide, talcum powder, and barium sulfate is 1:(0.3-0.6)(2.5-3):(3.5-4.5).

[0018] More preferably, the zinc oxide is a triazine graft-modified zinc oxide, and a preparation method thereof comprises: under a nitrogen atmosphere, adding cyanuric chloride into tetrahydrofuran and triethylamine, stirring, then adding a silane coupling agent dropwise, reacting at 4-5°C for 2-3h, then adding 2-(2'-hydroxy-5'-methylphenyl)benzotriazole into the reaction system, then increasing the temperature at a rate of 4°C / min until 60-75°C, reacting for 2-3h, then performing suction filtration, reducing pressure distillation, and recrystallization to obtain a silicon-based triazine compound;

[0019] ZnO is dispersed in 300mL of ethanol, ultrasonic treatment is performed for 30min to obtain a ZnO suspension; the silicon-based triazine compound is added into ethanol containing the ZnO suspension, glacial acetic acid is used to adjust the pH to 4-5, stirring is performed at 50-60°C for 4-6h, and then centrifugal drying is performed to obtain the triazine graft-modified zinc oxide.

[0020] By using the above technical solution, on the one hand, the rigid structure of the triazine ring can prevent the agglomeration of the fillers, and through the silicon-based grafting reaction, the phase separation of the fillers and the resin can be reduced, the surface properties such as leveling property and uniformity can be improved, and the water absorption of the zinc oxide in the water-based paint can be reduced, thereby improving the water resistance of the paint; on the other hand, the addition of 2-(2'-hydroxy-5'-methylphenyl)benzotriazole and the triazine structure together can not only improve the structural stability of the modified zinc oxide, but also form a complementation of the ultraviolet absorption effect, can expand the absorption range of ultraviolet rays, and improve the shielding effect of ultraviolet rays, thereby improving the aging resistance of the coating film.

[0021] The anti-rust pigment is one or more of zinc phosphate, aluminum tripolyphosphate, phosphomolybdic acid zinc aluminum, and iron titanium powder.

[0022] The rheological aid comprises one or both of organic bentonite and hydrogenated castor oil.

[0023] The anti-aging aid is a mixture of ultraviolet absorber 1, ultraviolet absorber 2, and ethylene glycol butyl ether at a mass ratio of 1:1:(0.5-1).

[0024] In a second aspect, the application provides a preparation process of a protective water-based paint with a one-step bottom surface based on dip coating, comprising the following steps: S1: mixing water and a part of the water-based epoxy ester resin, and stirring for 5-10min; then sequentially adding a water-based wetting dispersant and a defoaming agent to obtain a mixed slurry;

[0025] S2: adding an anti-rust pigment and fillers into the mixed slurry obtained in step S1, stirring, and then performing grinding to obtain a pigment and filler slurry;

[0026] S3: The remaining waterborne epoxy ester resin, amino resin and waterborne fluorocarbon resin are added to the pigment and filler slurry obtained in step S2, the waterborne additive is slowly added, and the aging-resistant additive, rheological additive, 1200-2000 r / min stirring is added in sequence, mixed uniformly, then the thickening agent is added, and the system viscosity is adjusted with water, and the stirring is completed;

[0027] S4: A component and B component are mixed uniformly at a ratio of (4.0-4.5):1 to obtain the protective one-coat water-based coating based on dipping.

[0028] The grinding temperature in the S2 step is 55-65℃, and the grinding fineness is 10-20μm.

[0029] In summary, the present application includes at least one of the following beneficial technical effects:

[0030] 1. The main resin is waterborne epoxy ester resin, amino resin and waterborne fluorocarbon resin, the waterborne epoxy ester resin containing epoxy group and ester group structure can crosslink with the amino group in the amino resin to form a stable three-dimensional network structure, which not only significantly improves the salt spray resistance of the coating, but also has good adhesion and chemical resistance, and optimizes the surface leveling property of the coating, making the coating surface smoother and more beautiful, and improving the appearance of the water-based coating. The addition of waterborne fluorocarbon resin containing fluorocarbon bond with strong chemical stability can effectively resist ultraviolet radiation, thereby greatly improving the aging resistance of the coating. In addition, the active groups of the waterborne epoxy ester resin and the hydroxyl groups in the waterborne fluorocarbon resin further crosslink to enhance the overall density of the coating, reduce the thickness of the coating while ensuring excellent protective performance of the coating. This composite system not only realizes the function of one-coat, but also meets the requirements of low energy consumption and high protection.

[0031] 2. The waterborne epoxy ester resin, amino resin and waterborne fluorocarbon resin in the present application work together to further enhance the overall protective performance of the coating, especially the aging resistance and salt spray resistance, effectively prolonging the service life of the coating. Not only does it retain the original excellent adhesion and chemical resistance of the epoxy resin, but also introduces acrylic monomers to improve the drying speed and weather resistance of the coating, and siloxane to improve salt spray resistance and barrier performance, avoiding brittle fracture. The phosphate group and the -CF3 group of the fluorocarbon resin can synergistically block water and oxygen penetration. Therefore, if the content of the modified waterborne epoxy ester resin is too low, the adhesion, salt spray resistance and leveling of the water-based coating will be reduced, which will affect the coating performance and long-term protective performance of the material. If the content of the amino resin is too low, it will affect the crosslinking of the amino resin with the waterborne epoxy ester resin to form a stable three-dimensional network structure, thereby reducing the hardness of the material and the surface performance of the coating.

[0032] 3. On the one hand, the rigid structure of the triazine ring can prevent the aggregation of fillers, reduce the phase separation of fillers and resins through silicon-based grafting reaction, improve the surface properties such as leveling property and uniformity, and reduce the water absorption of zinc oxide in water-based paint, thereby improving the water resistance of the paint; on the other hand, the addition of 2-(2'-hydroxy-5'-methylphenyl) benzotriazole and the triazine structure together can not only improve the structural stability of the modified zinc oxide, but also form a complementary effect of ultraviolet absorption, expand the absorption range of ultraviolet rays, and improve the shielding effect of ultraviolet rays, thereby improving the aging resistance of the coating film. DETAILED DESCRIPTION

[0033] Some raw materials in the examples and comparative examples in the present application: epoxy resin E-44; amino resin is methyl etherified amino resin CYMEL 327; water-based fluorocarbon resin is Lumiflon LF-200F; water-based wetting dispersant is BYK-154; defoaming agent is silicone-based defoaming agent BYK-1785; rheological aid is hydrogenated castor oil; thickening agent is bentonite; water-based aid is dodecanol ester; antirust pigment is zinc phosphate and aluminum tripolyphosphate with a mass ratio of 1:1; ultraviolet absorber 1 is Tinuvin 1130, Germany BASF; ultraviolet absorber 2 is Tinuvin 1130, Germany BASF; molecular weight regulator is α-methylstyrene dimer purchased from Macklin; carbon black is Cabot MONARCH 1400; zinc oxide is purchased from Shanghai Yuejiang Titanium White Chemical Products Co., Ltd.; talc powder specification 1250 mesh is purchased from Lingshou County Yongshun Mineral Product Processing Factory; barium sulfate is purchased from Langfang Shuangma Chemical Co., Ltd.; silane coupling agent is 3-aminopropyl triethoxysilane; curing agent is 8545 of Hexion; other raw materials can be obtained by market purchase.

[0034] Preparation Example 1

[0035] Preparation of modified water-based epoxy ester resin: (1) Mix 100 g of epoxy resin and 2 g of α-methylstyrene dimer with 24 g of linoleic acid, heat to 140℃ and stir for 5 min, and then cool to 90℃ to obtain an epoxy ester prepolymer;

[0036] (2) First, mix 8 g of VPA and 5 g of HEA, add APS 0.5 g, pre-emulsify for 15 min, then slowly drop 80 g of the epoxy ester prepolymer obtained in step (1) into the reaction system, react at 90℃ for 2 h, then add KH570 9 g and VPA 3 g, followed by adding APS 0.4 g, react at 85℃ for 1 h, cool to 50℃, adjust the pH to 9 with N,N-dimethyl ethanolamine, and adjust the solid content to 45% with water; to obtain a modified water-based epoxy ester resin.

[0037] Preparation Example 2

[0038] Preparation of modified waterborne epoxy ester resin: (1) 94 g of epoxy resin and 2 g of a-methylstyrene dimer were mixed with 30 g of linoleic acid, warmed to 140°C and stirred for 5 min, and then cooled to 90°C to obtain an epoxy ester prepolymer;

[0039] (2) First, 8 g of VPA and 5 g of HEA were mixed, 0.5 g of APS was added, pre-emulsified for 15 min, and then slowly added to 80 g of the epoxy ester prepolymer obtained in step (1), and reacted at 90°C for 2 h. Then, 9 g of KH570 and 3 g of VPA were added, followed by the addition of 0.4 g of APS, and reacted at 85°C for 1 h. After cooling to 50°C, N,N-dimethyl ethanolamine was used to adjust the pH to 9, and water was added to adjust the solid content to 45%. A modified waterborne epoxy ester resin was obtained.

[0040] Preparation Example 3

[0041] Preparation of modified waterborne epoxy ester resin: (1) 94 g of epoxy resin and 2 g of a-methylstyrene dimer were mixed with 30 g of linoleic acid, warmed to 140°C and stirred for 5 min, and then cooled to 90°C to obtain an epoxy ester prepolymer;

[0042] (2) First, 8 g of VPA and 5 g of HEA were mixed, 0.5 g of APS was added, pre-emulsified for 15 min, and then slowly added to 80 g of the epoxy ester prepolymer obtained in step (1), and reacted at 90°C for 2 h. Then, 9 g of KH570 and 3 g of VPA were added, followed by the addition of 0.4 g of APS, and reacted at 85°C for 1 h. After cooling to 50°C, N,N-dimethyl ethanolamine was used to adjust the pH to 9, and water was added to adjust the solid content to 45%. A modified waterborne epoxy ester resin was obtained.

[0043] Preparation Example 4

[0044] Preparation of modified waterborne epoxy ester resin: (1) 94 g of epoxy resin and 2 g of a-methylstyrene dimer were mixed with 30 g of linoleic acid, warmed to 140°C and stirred for 5 min, and then cooled to 90°C to obtain an epoxy ester prepolymer;

[0045] (2) First, 8 g of VPA and 5 g of HEA were mixed, 0.5 g of APS was added, pre-emulsified for 15 min, and then slowly added to 80 g of the epoxy ester prepolymer obtained in step (1), and reacted at 90°C for 2 h. Then, 9 g of KH570 and 3 g of VPA were added, followed by the addition of 0.4 g of APS, and reacted at 85°C for 1 h. After cooling to 50°C, N,N-dimethyl ethanolamine was used to adjust the pH to 9, and water was added to adjust the solid content to 45%. A modified waterborne epoxy ester resin was obtained.

[0046] Preparation Example 5

[0047] Preparation of the aqueous epoxy ester resin: (1) 100 g of the epoxy resin and 2 g of α-methyl styrene dimer were mixed with 24 g of linoleic acid, warmed to 140°C and stirred for 5 min, and then cooled to 90°C to obtain the aqueous epoxy ester resin.

[0048] Preparation Example 6

[0049] Preparation of the triazine grafted modified zinc oxide: 4 g of cyanuric chloride was added to 38 mL of tetrahydrofuran and 18 mL of triethylamine under a nitrogen atmosphere, stirred, and then 4.9 g of a silane coupling agent was added dropwise, reacted at 5°C for 3 h, 6.2 g of 2-(2'-hydroxy-5'-methylphenyl) benzotriazole was added to the reaction system, and then warmed at a rate of 4°C / min to 75°C and reacted for 3 h, filtered, distilled under reduced pressure, recrystallized with n-hexane to obtain a silane-based triazine compound;

[0050] 100 g of ZnO was dispersed in 300 mL of ethanol, ultrasonically treated for 30 min to obtain a ZnO suspension, 200 mL of ethanol containing 12 g of the silane-based triazine compound was added, the pH was adjusted to 5 with glacial acetic acid, stirred at 60°C for 4 h, centrifuged and washed, and then dried at 60°C under vacuum to obtain the triazine grafted modified zinc oxide.

[0051] Preparation Example 7

[0052] Preparation of the triazine grafted modified zinc oxide: 4 g of cyanuric chloride was added to 38 mL of tetrahydrofuran and 18 mL of triethylamine under a nitrogen atmosphere, stirred, and then 4.9 g of a silane coupling agent was added dropwise, reacted at 5°C for 3 h, 6.2 g of ethylene glycol was added to the reaction system, and then warmed at a rate of 4°C / min to 75°C and reacted for 3 h, filtered, distilled under reduced pressure, recrystallized with n-hexane to obtain a silane-based triazine compound; 100 g of ZnO was dispersed in 300 mL of ethanol, ultrasonically treated for 30 min to obtain a ZnO suspension, 200 mL of ethanol containing 12 g of the silane-based triazine compound was added, the pH was adjusted to 5 with glacial acetic acid, stirred at 60°C for 4 h, centrifuged and washed, and then dried at 60°C under vacuum to obtain the triazine grafted modified zinc oxide.

[0053] Example 1

[0054] A kind of protective bottom surface integration water-based paint based on dip coating, water-based paint includes A component and B component;A component includes the following weight parts of raw materials: main resin 656.5g, water 34g, water-based wet dispersant 7g, defoaming agent 0.6g, filler 262.1g, water-based auxiliary 2g, anti-aging auxiliary 10.5g, anti-rust pigment 38.2g, rheological auxiliary 5g, thickening agent 10g;Main resin is the water-based epoxy ester resin, amino resin and water-based fluorocarbon resin prepared in preparation example 1;B component includes curing agent;Filler is carbon black, zinc oxide, talcum powder, barium sulfate with mass ratio of 1:0.35:2.6:4.1;Anti-aging auxiliary is 3.5g ultraviolet absorber 1 and 3.5g ultraviolet absorber 2 diluted with 3.5g ethylene glycol butyl ether.

[0055] Preparation process is as follows: S1: 15g water and 394g water-based epoxy ester resin prepared in preparation example 1 are mixed, stirring for 10min;Then 7g water-based wet dispersant, 0.6g defoaming agent are added in turn, stirring for 10min to obtain mixed slurry;

[0056] S2: according to the proportion, carbon black, zinc oxide, anti-rust pigment, talcum powder and barium sulfate are added into the mixed slurry obtained in step S1, and then stirring and grinding are carried out, the grinding temperature is 65℃, and the grinding is carried out until the fineness is 20 μm to obtain pigment and filler slurry;

[0057] S3: the remaining 142.9g water-based epoxy ester resin prepared in preparation example 1, 79.7g amino resin and 39.9g water-based fluorocarbon resin are added into the pigment and filler slurry obtained in step S2, and then water-based auxiliary is slowly added according to the proportion, anti-aging auxiliary and rheological auxiliary are added in turn under the condition of stirring at 1200r / min, and then stirring is carried out until they are uniformly mixed, 10g thickening agent is added, 19g water is used to adjust the viscosity of the system, and then stirring is completed to obtain A component;

[0058] S4: A component and B component are uniformly mixed according to the proportion to obtain protective bottom surface integration water-based paint based on dip coating.

[0059] Example 2

[0060] A kind of protective bottom surface integration water-based paint based on dip coating, water-based paint includes A component and B component;A component includes the following weight parts of raw materials: main resin 656.5g, water 34g, water-based wet dispersant 7g, defoaming agent 0.6g, filler 262.1g, water-based auxiliary 2g, anti-aging auxiliary 10.5g, anti-rust pigment 38.2g, rheological auxiliary 5g, thickening agent 10g;Main resin is the water-based epoxy ester resin, amino resin and water-based fluorocarbon resin prepared in preparation example 1;B component includes curing agent;Filler is carbon black, zinc oxide, talcum powder, barium sulfate with mass ratio of 1:0.35:2.6:4.1;Anti-aging auxiliary is 3.5g ultraviolet absorber 1 and 3.5g ultraviolet absorber 2 diluted with 3.5g ethylene glycol butyl ether.

[0061] The preparation process is as follows: S1: 15 g of water and 367.2 g of the water-based epoxy ester resin prepared in Preparation Example 1 are mixed, and stirred for 10 min; then 7 g of a water-based wetting dispersant and 0.6 g of a defoaming agent are sequentially added, and stirred for 10 min to obtain a mixed slurry;

[0062] S2: according to the proportion, carbon black, zinc oxide, anti-rust pigment, talc and barium sulfate are added to the mixed slurry obtained in step S1, and after stirring, grinding is performed, the grinding temperature is 65°C, and the grinding is performed until the fineness is 20 μm to obtain a pigment and filler slurry;

[0063] S3: the remaining 142.9 g of the water-based epoxy ester resin prepared in Preparation Example 1, 79.7 g of an amino resin and 63.7 g of a water-based fluorocarbon resin are added to the pigment and filler slurry obtained in step S2, and according to the proportion, a water-based auxiliary agent is slowly added, and then an anti-aging auxiliary agent and a rheological auxiliary agent are sequentially added under stirring at 1200 r / min, and then mixed uniformly, and then 10 g of a thickening agent is added, and then 19 g of water is added to adjust the viscosity of the system, and then stirring is completed to obtain component A;

[0064] S4: component A and component B are mixed according to the proportion to obtain a protective one-coat water-based paint based on dipping.

[0065] Example 3

[0066] A protective one-coat water-based paint based on dipping, the water-based paint comprising component A and component B; component A comprises the following raw materials in parts by weight: 573.9 g of a main body resin, 34 g of water, 7 g of a water-based wetting dispersant, 0.6 g of a defoaming agent, 344.7 g of a filler, 2 g of a water-based auxiliary agent, 10.5 g of an anti-aging auxiliary agent, 38.2 g of an anti-rust pigment, 5 g of a rheological auxiliary agent, and 10 g of a thickening agent; the main body resin is a water-based epoxy ester resin, an amino resin and a water-based fluorocarbon resin prepared in Preparation Example 1; component B comprises a curing agent; the filler is carbon black, zinc oxide, talc and barium sulfate with a mass ratio of 1:0.35:2.6:4.1; the anti-aging auxiliary agent is 3.5 g of ultraviolet absorber 1 and 3.5 g of ultraviolet absorber 2 diluted with 3.5 g of ethylene glycol butyl ether.

[0067] The preparation process is as follows: S1: 15 g of water and 394 g of the water-based epoxy ester resin prepared in Preparation Example 1 are mixed, and stirred for 10 min; then 7 g of a water-based wetting dispersant and 0.6 g of a defoaming agent are sequentially added, and stirred for 10 min to obtain a mixed slurry;

[0068] S2: according to the proportion, carbon black, zinc oxide, anti-rust pigment, talc and barium sulfate are added to the mixed slurry obtained in step S1, and after stirring, grinding is performed, the grinding temperature is 65°C, and the grinding is performed until the fineness is 20 μm to obtain a pigment and filler slurry;

[0069] S3: Add the remaining 142.9 g of the waterborne epoxy ester resin prepared in Preparation Example 1, 79.7 g of the amino resin, and 39.9 g of the waterborne fluorocarbon resin into the pigment and filler slurry obtained in step S2, slowly add the waterborne adjuvant in proportion, and then sequentially add the anti-aging adjuvant and the rheological adjuvant under stirring at 1200 r / min, mix uniformly, add 10 g of the thickening agent, adjust the viscosity of the system with 19 g of water, and complete stirring to obtain the A component;

[0070] S4: Mix the A component and the B component uniformly in proportion to obtain the protective one-coat waterborne coating based on immersion coating.

[0071] Example 4

[0072] A protective one-coat waterborne coating based on immersion coating, which comprises an A component and a B component; the A component comprises the following raw materials in parts by weight: 656.5 g of the main body resin, 34 g of water, 7 g of the waterborne wet dispersant, 0.6 g of the defoaming agent, 262.1 g of the filler, 2 g of the waterborne adjuvant, 10.5 g of the anti-aging adjuvant, 38.2 g of the anti-rust pigment, 5 g of the rheological adjuvant, and 10 g of the thickening agent; the main body resin is the waterborne epoxy ester resin, the amino resin, and the waterborne fluorocarbon resin prepared in Preparation Example 2; the B component comprises a curing agent; the filler is carbon black, zinc oxide, talc, and barium sulfate in a mass ratio of 1:0.35:2.6:4.1; the anti-aging adjuvant is 3.5 g of ultraviolet absorber 1 and 3.5 g of ultraviolet absorber 2 diluted with 3.5 g of ethylene glycol butyl ether.

[0073] The preparation process is as follows: S1: Mix 15 g of water and 394 g of the waterborne epoxy ester resin prepared in Preparation Example 2, and stir for 10 min; then sequentially add 7 g of the waterborne wet dispersant and 0.6 g of the defoaming agent, and stir for 10 min to obtain a mixed slurry;

[0074] S2: In proportion, add carbon black, zinc oxide, anti-rust pigment, talc, and barium sulfate into the mixed slurry obtained in step S1, stir, and then perform grinding; the grinding temperature is 65°C, and the grinding is performed until the fineness is 20 μm to obtain a pigment and filler slurry;

[0075] S3: Add the remaining 142.9 g of the waterborne epoxy ester resin prepared in Preparation Example 2, 79.7 g of the amino resin, and 39.9 g of the waterborne fluorocarbon resin into the pigment and filler slurry obtained in step S2, slowly add the waterborne adjuvant in proportion, and then sequentially add the anti-aging adjuvant and the rheological adjuvant under stirring at 1200 r / min, mix uniformly, add 10 g of the thickening agent, adjust the viscosity of the system with 19 g of water, and complete stirring to obtain the A component;

[0076] S4: Mix the A component and the B component uniformly in proportion to obtain the protective one-coat waterborne coating based on immersion coating.

[0077] Example 5

[0078] A kind of protective bottom surface integration water-based paint based on dip coating, water-based paint includes A component and B component;A component includes the following weight parts of raw materials: main resin 656.5g, water 34g, water-based wet dispersant 7g, defoaming agent 0.6g, filler 262.1g, water-based auxiliary 2g, anti-aging auxiliary 10.5g, anti-rust pigment 38.2g, rheological auxiliary 5g, thickening agent 10g;Main resin is the water-based epoxy ester resin, amino resin and water-based fluorocarbon resin prepared in preparation example 3;B component includes curing agent;Filler is carbon black, zinc oxide, talcum powder, barium sulfate with mass ratio of 1:0.35:2.6:4.1;Anti-aging auxiliary is 3.5g ultraviolet absorber 1 and 3.5g ultraviolet absorber 2 diluted with 3.5g ethylene glycol butyl ether.

[0079] Preparation process is as follows: S1: 15g water and 394g water-based epoxy ester resin prepared in preparation example 3 are mixed, stirring 10min;Then 7g water-based wet dispersant, 0.6g defoaming agent are added in turn, stirring 10min to obtain mixed slurry;

[0080] S2: according to the proportion, carbon black, zinc oxide, anti-rust pigment, talcum powder and barium sulfate are added into the mixed slurry obtained in step S1, after stirring, grinding is carried out, the grinding temperature is 65℃, grinding is carried out until the fineness is 20 μm, to obtain pigment and filler slurry;

[0081] S3: the remaining 142.9g water-based epoxy ester resin prepared in preparation example 3, 79.7g amino resin and 39.9g water-based fluorocarbon resin are added into the pigment and filler slurry obtained in step S2, according to the proportion, water-based auxiliary is slowly added, 1200r / min stirring, anti-aging auxiliary, rheological auxiliary are added in turn, mixing is uniform, then 10g thickening agent is added, 19g water is used to adjust the viscosity of the system, stirring is completed to obtain A component;

[0082] S4: A component and B component are mixed uniformly according to the proportion to obtain protective bottom surface integration water-based paint based on dip coating.

[0083] Example 6

[0084] A kind of protective bottom surface integration water-based paint based on dip coating, water-based paint includes A component and B component;A component includes the following weight parts of raw materials: main resin 656.5g, water 34g, water-based wet dispersant 7g, defoaming agent 0.6g, filler 262.1g, water-based auxiliary 2g, anti-aging auxiliary 10.5g, anti-rust pigment 38.2g, rheological auxiliary 5g, thickening agent 10g;Main resin is the water-based epoxy ester resin, amino resin and water-based fluorocarbon resin prepared in preparation example 4;B component includes curing agent;Filler is carbon black, zinc oxide, talcum powder, barium sulfate with mass ratio of 1:0.35:2.6:4.1;Anti-aging auxiliary is 3.5g ultraviolet absorber 1 and 3.5g ultraviolet absorber 2 diluted with 3.5g ethylene glycol butyl ether.

[0085] The preparation process is as follows: S1: 15 g of water and 394 g of the waterborne epoxy ester resin prepared in Preparation Example 4 are mixed, and stirred for 10 min; then 7 g of a waterborne wetting dispersant and 0.6 g of a defoaming agent are sequentially added, and stirred for 10 min to obtain a mixed slurry;

[0086] S2: according to the proportion, carbon black, zinc oxide, anti-rust pigment, talcum powder and barium sulfate are added to the mixed slurry obtained in step S1, and after stirring, grinding is performed, the grinding temperature is 65°C, and the grinding is performed until the fineness is 20 μm to obtain a pigment and filler slurry;

[0087] S3: the remaining 142.9 g of the waterborne epoxy ester resin prepared in Preparation Example 4, 79.7 g of an amino resin and 39.9 g of a waterborne fluorocarbon resin are added to the pigment and filler slurry obtained in step S2, and according to the proportion, a waterborne auxiliary agent is slowly added, and an anti-aging auxiliary agent and a rheological auxiliary agent are sequentially added under stirring at 1200 r / min, and then mixed uniformly, and then 10 g of a thickening agent is added, and 19 g of water is used to adjust the viscosity of the system, and stirring is completed to obtain component A;

[0088] S4: component A is uniformly mixed with component B according to the proportion to obtain a protective one-coat waterborne coating based on immersion coating.

[0089] Example 7

[0090] A protective one-coat waterborne coating based on immersion coating, the waterborne coating comprising component A and component B; component A comprises the following raw materials in parts by weight: 656.5 g of a main body resin, 34 g of water, 7 g of a waterborne wetting dispersant, 0.6 g of a defoaming agent, 262.1 g of a filler, 2 g of a waterborne auxiliary agent, 10.5 g of an anti-aging auxiliary agent, 38.2 g of an anti-rust pigment, 5 g of a rheological auxiliary agent, and 10 g of a thickening agent; the main body resin is a waterborne epoxy ester resin, an amino resin and a waterborne fluorocarbon resin prepared in Preparation Example 5; component B comprises a curing agent; the filler is carbon black, zinc oxide, talcum powder and barium sulfate with a mass ratio of 1:0.35:2.6:4.1; the anti-aging auxiliary agent is 3.5 g of ultraviolet absorber 1 and 3.5 g of ultraviolet absorber 2 diluted with 3.5 g of ethylene glycol butyl ether.

[0091] The preparation process is as follows: S1: 15 g of water and 394 g of the waterborne epoxy ester resin prepared in Preparation Example 4 are mixed, and stirred for 10 min; then 7 g of a waterborne wetting dispersant and 0.6 g of a defoaming agent are sequentially added, and stirred for 10 min to obtain a mixed slurry;

[0092] S2: according to the proportion, carbon black, zinc oxide, anti-rust pigment, talcum powder and barium sulfate are added to the mixed slurry obtained in step S1, and after stirring, grinding is performed, the grinding temperature is 65°C, and the grinding is performed until the fineness is 20 μm to obtain a pigment and filler slurry;

[0093] S3: Add the remaining 142.9 g of the waterborne epoxy ester resin prepared in Preparation Example 1, 79.7 g of the amino resin, and 39.9 g of the waterborne fluorocarbon resin into the pigment and filler slurry obtained in step S2, slowly add the waterborne adjuvant in proportion, and then sequentially add the anti-aging adjuvant, the rheological adjuvant, and mix them uniformly under stirring at 1200 r / min, and then add 10 g of the thickening agent, adjust the viscosity of the system with 19 g of water, and complete the stirring to obtain the A component;

[0094] S4: Mix the A component and the B component uniformly in proportion to obtain the protective one-coat waterborne paint based on dipping.

[0095] Example 8

[0096] A protective one-coat waterborne paint based on dipping, which comprises an A component and a B component; the A component comprises the following raw materials in parts by weight: 656.5 g of the main body resin, 34 g of water, 7 g of the waterborne wet dispersant, 0.6 g of the defoaming agent, 262.1 g of the filler, 2 g of the waterborne adjuvant, 10.5 g of the anti-aging adjuvant, 38.2 g of the anti-rust pigment, 5 g of the rheological adjuvant, and 10 g of the thickening agent; the main body resin is the waterborne epoxy ester resin, the amino resin, and the waterborne fluorocarbon resin prepared in Preparation Example 1; the B component comprises a curing agent; the filler is carbon black, zinc oxide prepared in Preparation Example 6, talcum powder, and barium sulfate; the anti-aging adjuvant is 3.5 g of ultraviolet absorber 1 and 3.5 g of ultraviolet absorber 2 diluted with 3.5 g of ethylene glycol butyl ether.

[0097] The preparation process is as follows: S1: mix 15 g of water and 394 g of the waterborne epoxy ester resin prepared in Preparation Example 1, and stir for 10 min; then sequentially add 7 g of the waterborne wet dispersant and 0.6 g of the defoaming agent, and stir for 10 min to obtain a mixed slurry;

[0098] S2: add carbon black, zinc oxide prepared in Preparation Example 6, the anti-rust pigment, talcum powder, and barium sulfate into the mixed slurry obtained in step S1 in proportion, and then perform grinding after stirring; the grinding temperature is 65°C, and the grinding is performed until the fineness is 20 μm to obtain a pigment and filler slurry; S3: add the remaining 142.9 g of the waterborne epoxy ester resin prepared in Preparation Example 1, 79.7 g of the amino resin, and 39.9 g of the waterborne fluorocarbon resin into the pigment and filler slurry obtained in step S2, slowly add the waterborne adjuvant in proportion, and then sequentially add the anti-aging adjuvant, the rheological adjuvant, and mix them uniformly under stirring at 1200 r / min, and then add 10 g of the thickening agent, adjust the viscosity of the system with 19 g of water, and complete the stirring to obtain the A component;

[0099] S4: Mix the A component and the B component uniformly in proportion to obtain the protective one-coat waterborne paint based on dipping.

[0100] Example 9

[0101] A kind of protective bottom surface integration water-based paint based on dip coating, water-based paint includes A component and B component;A component includes the following weight parts of raw materials: main body resin 656.5g, water 34g, water-based wet dispersant 7g, defoaming agent 0.6g, filler 262.1g, water-based auxiliary 2g, anti-aging auxiliary 10.5g, anti-rust pigment 38.2g, rheological auxiliary 5g, thickening agent 10g;Main body resin is the water-based epoxy ester resin, amino resin and water-based fluorocarbon resin prepared in preparation example 1;B component includes curing agent;Filler is carbon black, zinc oxide prepared in preparation example 7, talcum powder, barium sulfate;Anti-aging auxiliary is 3.5g UV absorber 1 and 3.5g UV absorber 2 diluted with 3.5g ethylene glycol butyl ether.

[0102] Preparation process is: S1: 15g water and 394g water-based epoxy ester resin prepared in preparation example 1 are mixed, stirring 10 min;Then 7g water-based wet dispersant, 0.6g defoaming agent are added in turn, stirring 10 min to obtain mixed slurry;

[0103] S2: according to the proportion, carbon black, zinc oxide prepared in preparation example 7, anti-rust pigment, talcum powder and barium sulfate are added into the mixed slurry obtained in step S1, and after stirring, grinding is carried out, the grinding temperature is 65 DEG C, and the grinding is carried out until the fineness is 20 μm, to obtain pigment and filler slurry;S3: the remaining 142.9g water-based epoxy ester resin prepared in preparation example 1, 79.7g amino resin and 39.9g water-based fluorocarbon resin are added into the pigment and filler slurry obtained in step S2, and according to the proportion, water-based auxiliary is slowly added, and 1200r / min stirring is carried out, and then anti-aging auxiliary, rheological auxiliary are added in turn, and then 10g thickening agent is added, and 19g water is used to adjust the viscosity of the system, and stirring is completed to obtain A component;

[0104] S4: A component and B component are mixed uniformly according to the proportion to obtain protective bottom surface integration water-based paint based on dip coating.

[0105] Example 10

[0106] A kind of protective bottom surface integration water-based paint based on dip coating, water-based paint includes A component and B component;A component includes the following weight parts of raw materials: main body resin 656.5g, water 34g, water-based wet dispersant 7g, defoaming agent 0.6g, filler 262.1g, water-based auxiliary 2g, anti-aging auxiliary 10.5g, anti-rust pigment 38.2g, rheological auxiliary 5g, thickening agent 10g;Main body resin is the water-based epoxy ester resin, amino resin and water-based fluorocarbon resin prepared in preparation example 1;B component includes curing agent;Filler is carbon black, talcum powder, barium sulfate with mass ratio of 1.35:2.6:4.1;Anti-aging auxiliary is 3.5g UV absorber 1 and 3.5g UV absorber 2 diluted with 3.5g ethylene glycol butyl ether.

[0107] Preparation process is: S1: 15g water and 394g water-based epoxy ester resin prepared in preparation example 1 are mixed, and stirred for 10min; then 7g water-based wet dispersant, 0.6g defoaming agent are added in sequence, and stirred for 10min to obtain a mixed slurry;

[0108] S2: according to the proportion, carbon black, anti-rust pigment, talcum powder and barium sulfate are added into the mixed slurry obtained in step S1, and after stirring, grinding is carried out, the grinding temperature is 65℃, and the grinding is carried out until the fineness is 20μm to obtain a pigment and filler slurry;

[0109] S3: the remaining 142.9g water-based epoxy ester resin prepared in preparation example 1, 79.7g amino resin and 39.9g water-based fluorocarbon resin are added into the pigment and filler slurry obtained in step S2, water-based auxiliary agent is slowly added according to the proportion, and then aging-resistant auxiliary agent and rheological auxiliary agent are added in sequence under the condition of stirring at 1200r / min, and then mixed uniformly, 10g thickening agent is added, 19g water is used to adjust the viscosity of the system, and stirring is completed to obtain component A;

[0110] S4: component A and component B are mixed uniformly according to the proportion to obtain a protective one-coat water-based paint based on dipping.

[0111] Comparative example 1

[0112] A protective one-coat water-based paint based on dipping, the water-based paint comprising component A and component B; component A comprises the following raw materials in parts by weight: main body resin 656.5g, water 34g, water-based wet dispersant 7g, defoaming agent 0.6g, filler 262.1g, water-based auxiliary agent 2g, aging-resistant auxiliary agent 10.5g, anti-rust pigment 38.2g, rheological auxiliary agent 5g, thickening agent 10g; the main body resin is water-based epoxy ester resin prepared in preparation example 1; component B comprises a curing agent; the filler is carbon black, zinc oxide, talcum powder and barium sulfate with a mass ratio of 1:0.35:2.6:4.1; the aging-resistant auxiliary agent is 3.5g ultraviolet absorber 1 and 3.5g ultraviolet absorber 2 diluted with 3.5g ethylene glycol butyl ether.

[0113] Preparation process is: S1: 15g water and 394g water-based epoxy ester resin prepared in preparation example 1 are mixed, and stirred for 10min; then 7g water-based wet dispersant, 0.6g defoaming agent are added in sequence, and stirred for 10min to obtain a mixed slurry;

[0114] S2: according to the proportion, carbon black, anti-rust pigment, talcum powder and barium sulfate are added into the mixed slurry obtained in step S1, and after stirring, grinding is carried out, the grinding temperature is 65℃, and the grinding is carried out until the fineness is 20μm to obtain a pigment and filler slurry;

[0115] S3: The remaining 142.9 g of the waterborne epoxy ester resin prepared in Preparation Example 1 was added to the pigment and filler slurry obtained in step S2, and waterborne adjuvant was slowly added in proportion. After stirring at 1200 r / min, aging-resistant adjuvant and rheological adjuvant were sequentially added and mixed uniformly. Then, 10 g of thickening agent was added, 19 g of water was used to adjust the viscosity of the system, and stirring was completed to obtain component A;

[0116] S4: Component A and component B were mixed uniformly in proportion to obtain a protective one-coat waterborne coating based on immersion coating.

[0117] Comparative Example 2

[0118] A protective one-coat waterborne coating based on immersion coating, the waterborne coating comprising component A and component B; component A comprises the following raw materials in parts by weight: 656.5 g of main resin, 34 g of water, 7 g of waterborne wet dispersant, 0.6 g of defoaming agent, 262.1 g of filler, 2 g of waterborne adjuvant, 10.5 g of aging-resistant adjuvant, 38.2 g of anti-rust pigment, 5 g of rheological adjuvant, and 10 g of thickening agent; the main resin is a waterborne epoxy ester resin and an amino resin prepared in Preparation Example 1; component B comprises a curing agent; the filler is carbon black, zinc oxide, talc, and barium sulfate in a mass ratio of 1:0.35:2.6:4.1; the aging-resistant adjuvant is 3.5 g of ultraviolet absorber 1 and 3.5 g of ultraviolet absorber 2 diluted with 3.5 g of ethylene glycol butyl ether.

[0119] The preparation process is as follows: S1: 15 g of water and 433.9 g of the waterborne epoxy ester resin prepared in Preparation Example 1 were mixed and stirred for 10 min; then 7 g of waterborne wet dispersant and 0.6 g of defoaming agent were sequentially added and stirred for 10 min to obtain a mixed slurry;

[0120] S2: In proportion, carbon black, zinc oxide, anti-rust pigment, talc, and barium sulfate were added to the mixed slurry obtained in step S1, and after stirring, they were ground at a grinding temperature of 65°C until the fineness was 20 μm to obtain a pigment and filler slurry;

[0121] S3: The remaining 142.9 g of the waterborne epoxy ester resin prepared in Preparation Example 1 and 79.7 g of the amino resin were added to the pigment and filler slurry obtained in step S2, and waterborne adjuvant was slowly added in proportion. After stirring at 1200 r / min, aging-resistant adjuvant and rheological adjuvant were sequentially added and mixed uniformly. Then, 10 g of thickening agent was added, 19 g of water was used to adjust the viscosity of the system, and stirring was completed to obtain component A;

[0122] S4: Component A and component B were mixed uniformly in proportion to obtain a protective one-coat waterborne coating based on immersion coating.

[0123] Comparative Example 3

[0124] A kind of protective bottom surface integration water-based paint based on dip coating, water-based paint includes A component and B component;A component includes the following weight parts of raw materials: main body resin 656.5g, water 34g, water-based wet dispersant 7g, defoaming agent 0.6g, filler 262.1g, water-based auxiliary 2g, anti-aging auxiliary 10.5g, antirust pigment 38.2g, rheological auxiliary 5g, thickening agent 10g;Main body resin is the water-based epoxy ester resin and water-based fluorocarbon resin prepared in preparation example 1;B component includes curing agent;Filler is the mass ratio of 1:0.35:2.6:4.1 of carbon black, zinc oxide, talcum powder, barium sulfate;Anti-aging auxiliary is 3.5g ultraviolet absorber 1 and 3.5g ultraviolet absorber 2 diluted with 3.5g ethylene glycol butyl ether.

[0125] Preparation process is as follows: S1: 15g water and 473.7g water-based epoxy ester resin prepared in preparation example 1 are mixed, stirring 10min;Then 7g water-based wet dispersant, 0.6g defoaming agent are added in turn, stirring 10min to obtain mixed slurry;

[0126] S2: according to the proportion, carbon black, zinc oxide, antirust pigment, talcum powder and barium sulfate are added into the mixed slurry obtained in step S1, and after stirring, grinding is carried out, the grinding temperature is 65℃, and the grinding is carried out until the fineness is 20 μm to obtain pigment and filler slurry;

[0127] S3: the remaining 142.9g water-based epoxy ester resin prepared in preparation example 1 and 39.9g water-based fluorocarbon resin are added into the pigment and filler slurry obtained in step S2, the water-based auxiliary is slowly added according to the proportion, the anti-aging auxiliary, the rheological auxiliary are added in turn under the condition of stirring at 1200r / min, and then the thickening agent is added, the system viscosity is adjusted with 19g water, and the stirring is completed to obtain A component;

[0128] S4: A component and B component are mixed uniformly according to the proportion to obtain protective bottom surface integration water-based paint based on dip coating.

[0129] Comparative example 4

[0130] A kind of protective bottom surface integration water-based paint based on dip coating, water-based paint includes A component and B component;A component includes the following weight parts of raw materials: main body resin 656.5g, water 44.5g, water-based wet dispersant 7g, defoaming agent 0.6g, filler 262.1g, water-based auxiliary 2g, antirust pigment 38.2g, rheological auxiliary 5g, thickening agent 10g;Main body resin is the water-based epoxy ester resin, amino resin and water-based fluorocarbon resin prepared in preparation example 1;B component includes curing agent;Filler is the mass ratio of 1:0.35:2.6:4.1 of carbon black, zinc oxide, talcum powder, barium sulfate.

[0131] The preparation process is as follows: S1: 15 g of water and 394 g of the waterborne epoxy ester resin prepared in Preparation Example 1 are mixed, and stirred for 10 min; then 7 g of a waterborne wetting dispersant and 0.6 g of a defoaming agent are sequentially added, and stirred for 10 min to obtain a mixed slurry;

[0132] S2: according to the proportion, carbon black, zinc oxide, anti-rust pigment, talcum powder and barium sulfate are added to the mixed slurry obtained in step S1, and after stirring, grinding is performed, the grinding temperature is 65°C, and the grinding is performed until the fineness is 20 μm to obtain a pigment and filler slurry;

[0133] S3: the remaining 142.9 g of the waterborne epoxy ester resin prepared in Preparation Example 1, 79.7 g of an amino resin and 39.9 g of a waterborne fluorocarbon resin are added to the pigment and filler slurry obtained in step S2, and according to the proportion, a waterborne auxiliary agent is slowly added, and a rheological auxiliary agent is sequentially added under stirring at 1200 r / min, and then mixed uniformly, and then 10 g of a thickening agent is added, and the viscosity of the system is adjusted with 29.5 g of water, and stirring is completed to obtain component A;

[0134] S4: component A is mixed with component B according to the proportion to obtain a protective one-coat waterborne coating based on immersion coating.

[0135] Performance detection

[0136] The A component prepared in the examples and comparative examples is supplemented with water to adjust the viscosity to 120 s, and then mixed with component B according to the proportion of 4.2:1 to obtain a protective one-coat waterborne coating based on immersion coating, and the performance of the immersion film with a film thickness of 25 μm is tested by using the following methods:

[0137] The adhesion is tested by using a cross-hatch method according to GB / T 9286-1988, the hardness is determined by using a pencil method according to ASTM D3363-2005, the aging resistance of the coating is determined according to GB / T 23987-2009, and 400 h of non-foaming, non-falling and non-color change is qualified;

[0138] The salt spray resistance is determined according to GB / T 1771-2007, and 240 h of non-foaming, non-falling and non-color change is qualified;

[0139] The water resistance is determined according to GB / T 1733-1993, and 240 h of non-foaming, non-falling and non-color change is qualified; the results are shown in Table 1.

[0140]

[0141]

[0142] As shown in Table 1, the protective one-coat waterborne coating based on immersion coating in the above examples has significantly improved aging resistance and salt spray resistance, and thus the protection effect and service life of the coating are improved.

[0143] From Comparative Examples 1-7 and Comparative Examples 1-3, it can be seen that the main resin is a water-based epoxy ester resin, an amino resin and a water-based fluorocarbon resin, the water-based epoxy ester resin containing an epoxy group and an ester group structure can cross-link with the amino group in the amino resin to form a stable three-dimensional network structure, not only significantly improving the salt spray resistance of the coating, making the coating have good adhesion and chemical resistance, but also optimizing the surface leveling of the coating. The addition of water-based fluorocarbon resin can greatly improve the aging resistance of the coating. If the content of the modified water-based epoxy ester resin is too low, the adhesion, salt spray resistance and leveling of the water-based coating will be reduced, thereby affecting the coating performance and long-term protection performance of the material. If the content of the amino resin is too low, it will affect the cross-linking of the amino resin with the water-based epoxy ester resin to form a stable three-dimensional network structure, thereby reducing the hardness of the material and the surface performance of the coating.

[0144] By modifying the epoxy resin, the polymer chain segment containing phosphate ester side chain can form a coordination bond with the metal substrate, enhance the salt spray resistance and corrosion resistance, and optimize the interface bonding, enhance the leveling and adhesion of the water-based coating. The addition of VPA in two times can make the phosphate ester uniformly distributed, avoid local excess leading to agglomeration, and thereby affect the surface performance of the material, affect the leveling and stability of the coating and other coating properties.

[0145] From Comparative Example 1 and Examples 8-10, it can be seen that the zinc oxide triazine is grafted and modified, and the rigid structure of the triazine ring can prevent the agglomeration of the filler on one hand, and through the silicon-based grafting reaction, the phase separation of the filler and the resin can be reduced, the leveling, uniformity and other surface properties can be improved, and the aging resistance of the coating film can be improved. The substitution reaction of 2-(2'-hydroxy-5'-methylphenyl) benzotriazole with triazine structure not only improves the structural stability of the modified zinc oxide, but also forms a complement of ultraviolet absorption, has a wide absorption band, good heat resistance, strong anti-yellowing performance, improves the shielding effect of ultraviolet rays, and thereby improves the aging resistance of the coating film.

[0146] The above are preferred embodiments of the present application, and do not limit the protection scope of the present application, therefore: any equivalent changes made on the basis of the structure, shape, principle of the present application should be covered within the protection scope of the present application.

Claims

1. A dip-based protective, one-coat waterborne coating characterized in that, The water-based coating comprises component A and component B. Component A includes: 656.5g of main resin, 34g of water, 7g of water-based wetting and dispersing agent, 0.6g of defoamer, 262.1g of filler, 2g of dodecyl ester, 10.5g of anti-aging additive, 38.2g of anti-rust pigment, 5g of rheology modifier, and 10g of thickener. The main resin consists of 536.9g of water-based epoxy ester resin, 79.7g of amino resin, and 39.9g of water-based fluorocarbon resin. Component B includes a curing agent. The filler consists of carbon black, triazine-grafted modified zinc oxide, talc, and barium sulfate. Preparation of the waterborne epoxy ester resin: (1) Mix 100g of epoxy resin and 2g of α-methylstyrene dimer with 24g of linoleic acid, heat to 140℃ and stir for 5min, then cool to 90℃ to obtain epoxy ester prepolymer; (2) First mix 8g of VPA and 5g of HEA, add 0.5g of APS, pre-emulsify for 15min, then slowly add 80g of the epoxy ester prepolymer obtained in step (1), react at 90℃ for 2h, then add 9g of KH570 and 3g of VPA, then add 0.4g of APS, react at 85℃ for 1h, cool to 50℃, adjust the pH to 9 with N,N-dimethylethanolamine, and add water to adjust the solid content to 45%; to obtain waterborne epoxy ester resin; Preparation of triazine-grafted modified zinc oxide: Under a nitrogen atmosphere, 4 g of cyanuric chloride was added to 38 mL of tetrahydrofuran and 18 mL of triethylamine, and stirred. Then, 4.9 g of 3-aminopropyltriethoxysilane was added dropwise, and the mixture was reacted at 5 °C for 3 h. 6.2 g of 2-(2'-hydroxy-5'-methylphenyl)benzotriazole was then added to the reaction system, and the temperature was increased at a rate of 4 °C / min until it reached 75 °C and reacted for 3 h. The mixture was filtered, distilled under reduced pressure, and recrystallized from n-hexane to obtain a silane-based triazine compound. 100 g of ZnO was dispersed in 300 mL of ethanol and sonicated for 30 min to obtain a ZnO suspension. 200 mL of ethanol containing 12 g of the silane-based triazine compound was added, and the pH was adjusted to 5 with glacial acetic acid. The mixture was stirred at 60 °C for 4 h, centrifuged and washed, and then vacuum dried at 60 °C to obtain triazine-grafted modified zinc oxide.

2. The process for the preparation of a dip-coating based protective one-coat waterborne coating according to claim 1, characterized in that, Includes the following steps: S1: Mix water and waterborne epoxy ester resin and stir for 10 minutes; then add waterborne wetting and dispersing agent and defoamer in sequence and stir for 10 minutes to obtain a mixed slurry; S2: Add carbon black, triazine-grafted modified zinc oxide, anti-rust pigment, talc powder and barium sulfate to the mixed slurry obtained in step S1, stir and grind to obtain pigment and filler slurry; S3: Add the remaining waterborne epoxy ester resin, amino resin and waterborne fluorocarbon resin to the pigment and filler slurry obtained in step S2, slowly add dodecyl alcohol ester, add anti-aging agent and rheology agent in sequence under stirring at 1200 r / min and mix evenly, then add thickener, adjust the viscosity of the system with water, and stir to obtain component A; S4: Component A and component B are mixed evenly to obtain a protective water-based coating that combines primer and topcoat based on dip coating.

3. A process for the preparation of a dip-coating based protective one-coat waterborne coating according to claim 2, characterized in that: In step S2, the grinding temperature is 65℃, and the grinding is carried out to a fineness of 20μm.

Images